A living anionic polymerization method is a polymerization method in which deactivation and side reactions such as chain transfer occur less frequently and which is suitable for controlling molecular weight of a polymer and performing the molecular design of primary structure of a block copolymer. Hence, in recent years, attention is paid to the living anionic polymerization method as a production process for polymers requiring molecular design that has been difficult in the conventional radical polymerization method such as block copolymer or graft copolymer useful for thermoplastic elastomer, polymer compatibilizer, and the like, telechelic polymer having reactive functional groups, and star polymer useful for use in paint resin and hotmelt adhesive and the like.
Examples of monomers capable of undergoing anionic polymerization include non-polar anionic polymerizable monomers such as styrene, butadiene, isoprene, and derivatives thereof; polar anionic polymerizable monomers such as methacrylic ester, acrylic ester, methacrylamide, acrylamide, methacrylonitrile, acrylonitrile, and derivatives thereof; and the like. The non-polar anionic polymerizable monomers are capable of undergoing anionic polymerization while maintaining a high level of living properties and have already been applied to industrial polymerization. On the other hand, in the polar anionic polymerizable monomers, an anionic species of polymerizable end generally undergoes a side reaction with a polar functional group (ester group, amide group, nitrile group, etc.) in the monomer during anionic polymerization. Accordingly, in order to allow living anionic polymerization of the polar anionic polymerizable monomers to proceed while suppressing the side reaction, the polymerization usually needs to be carried out under an extremely low temperature condition such as −78° C., which requires a large cooling system at the time of industrialization and presents a problem such as an increase in facility cost.
The process for polymerization reaction is classified into two: a batch process in which raw materials used are collectively fed into a polymerization reactor, the reaction mixture is taken out after completion of the reaction to and transferred to a polymer isolation step, and the polymerization reactor is washed as necessary to perform a next polymerization reaction; and a continuous process in which the raw materials are continuously fed into a polymerization rector and the reaction mixture is continuously taken out from the reaction system and transferred to a polymer isolation step. Of these processes, the continuous process is more effective in reducing facility cost and running cost and also more effective in improving productivity.
Examples of application of the continuous production process to living anionic polymerization of methacrylic ester or acrylic ester as a process for carrying out living anionic polymerization of the polar anionic polymerizable monomers include:    (1) a continuous production process by anionic polymerization using a static mixer-type reactor (refer to Patent Reference 1);    (2) a continuous anionic polymerization process for (meth) acrylic monomer using a micro mixer (refer to Patent Reference 2);    (3) a production process for star-branched acrylic polymers (refer to Patent Reference 3); and the like.
Patent Reference 1: JP-A No. 56910/1994
Patent Reference 2: Specification of U.S. Pat. No. 5,886,112
Patent Reference 3: Specification of U.S. Pat. No. 6,013,735
In Example 1 of the above (1), a poly(methyl methacrylate) (PMMA) having a narrow molecular weight distribution of 1.09 is obtained. However, the reaction temperature is as extremely low as −78° C., which makes it difficult to practice industrially. Although in the specification of the above (1), “−40° C. or lower is preferred for polar monomers such as methacrylate and acrylate” is described as a preferred reaction temperature, it is difficult to industrially adopt even −40° C. Further, only continuous polymerization of methyl methacrylate is described in Examples, and no example with an acrylic ester or no example of continuous production of a block copolymer is described.
In Examples of the above (2), the molecular weight distribution of obtained poly (methyl methacrylate) is from 1.48 to 2.44, which is wider compared with the molecular weight distribution of 1.01 to 1.20 for polymer obtained by conventional living anionic polymerization. Thus, the living properties of the polymerization process in the above (2) are insufficient, which makes it difficult to perform molecular design of copolymers such as block copolymer and graft copolymer and produce them in that process. In fact, although poly(tert-butyl acrylate)-b-poly(methyl methacrylate) is produced in Example 14, the molecular weight distribution of the obtained diblock copolymer is as wide as 2.05, and the molecular weight distribution cannot be narrowly controlled.
Further, in Examples of the above (3), the molecular weight distribution of the obtained star polymer is from 1.3 to 1.8, which is wider compared with the molecular weight distribution of 1.01 to 1.20 for polymer obtained by conventional living anionic polymerization. Thus, the living properties of the polymerization process in the above (3) are also insufficient.